KR20050024273A - Radiation curable coating composition - Google Patents

Abstract

The present invention relates to a radiation curable coating composition,

The radiation curable coating composition is (A) a compound represented by P- (D- (meth) acrylate) _n having a number average molecular weight (Mn) of 500 kg / kmol or more (wherein n is 2 to 40 and P is Is an oligomer or polymer backbone, and D comprises a urethane group and a heterocyclic group, said heterocyclic group having a Boltzmann average dipole moment of at least 2.5 dibi), and

(B) comprises a reactive diluent,

The heterocyclic group is preferably an oxazolidone group,

Moreover, this invention relates to the manufacturing method of the resin composition containing the compound containing an oxazolidone group and a (meth) acrylate group,

The method includes a reaction step of introducing a (meth) acrylate group into the compound, wherein the reaction step is carried out in the presence of an antioxidant.

Description

Radiation curable coating composition {RADIATION CURABLE COATING COMPOSITION}

The present invention relates to a radiation curable coating composition comprising a specific compound containing a urethane group and an acrylate group, a method for producing the compound, and a resin composition containing a compound obtainable by the method. The invention further relates to a group of specific compounds.

In the manufacture of optical fibers, a resin coating is applied immediately after drawing of the glass fibers for protection and reinforcement of the glass fibers. Generally, a soft primary coating layer of a flexible resin (low modulus and low Tg) coated directly on the glass surface and a second, relatively rigid resin applied over the first coating layer Two coatings are applied, a secondary coating layer (higher modulus and higher Tg). Often, for identification purposes, the ink will be further coated with an ink, the ink being a curable resin comprising colorants (eg pigments and / or dyes), or the second coating material being a colored second coating (ie colorant). It will be included).

Several coated (and optionally ink coated) optical fibers may be bundled to form so-called optical fiber ribbons, for example four or eight coated (and optionally ink coated) ) The optical fibers are arranged in a plane and tightly fixed with a binder to prepare a ribbon structure having a rectangular cross section. The binder material for binding several optical fibers to produce an optical fiber ribbon structure is called a ribbon matrix material. In addition, a material for further binding several optical fiber ribbons to produce a multi-core optical fiber ribbon is called a bundling material.

In order to obtain adequate protection and reinforcement of the glass fibers, good adhesion between the coating and the glass fibers is essential. Therefore, development of coating compositions that exhibit improved adhesion after application and curing to glass fibers is desirable.

Another very important property that is required nowadays for curable resins used as coating materials for optical fibers (for protection or identification) is a sufficiently fast cure rate, which is currently used and can be applied at an increased optical fiber drawing rate and at the same time thoroughly cured. To have. Currently, in the production of optical fibers and optical fiber assemblies, one of the limitations on how fast a production line can be operated is the rate of cure of the coating and / or binder. Therefore, development of coatings and / or binders with faster curing rates is desirable. In addition, the improved cure rate should be obtained without sacrificing the chemical and mechanical properties of the cured coating.

In addition to having a fast cure rate, the coating material exhibits many other requirements, in particular: very little physical change over long periods of time and also over a wide temperature range; Have acceptable heat resistance, light resistance (and thus exhibit acceptable aging properties such as low degree of yellowing), hydrolysis resistance, oil resistance and chemical resistance (such as acids and alkalis); Moisture and water only absorb relatively small amounts; It would also be desirable to satisfy little to no hydrogen gas that adversely affects the optical fibers.

Resins that are cured by exposure to radiation, such as ultraviolet light, are useful in the industry because of their rapid cure, the coated fibers can be produced at a rapid rate. In many of these radiation curable resin compositions, urethane oligomers having a polymer backbone and reactive end groups (eg, acrylate or methacrylate functionality, hereinafter referred to as (meth) acrylate functionality) are used. . In general, the composition will further comprise a reactive diluent, a photoinitiator, and optionally a suitable additive.

It is an object of the present invention to provide a radiation curable coating composition suitable for coating of optical glass fibers which exhibits very good adhesion to the optical glass fibers after curing.

A further object is to provide a radiation curable coating composition which exhibits a rapid curing rate upon exposure to radiation.

In US-3,979,406 the preparation of a group of compounds comprising oxazolidone groups, urethane groups and acrylate groups is known. Only general uses of these compounds are mentioned.

Summary of the Invention

The present invention further provides a radiation curable coating composition comprising the following components (A) and (B):

(A) A compound having a number average molecular weight of 500 kg / kmol or more and represented by P- (D-acrylate) _n , wherein n is 2 to 40, P is an oligomer or a polymer backbone, and D is a urethane group and a hetero A cyclic group, said heterocyclic group having a Boltzmann average dipole moment of at least 2.5 Debye; and

(B) reactive diluents.

The present invention provides a radiation curable coating composition comprising the following components (A) and (B):

(A) a compound containing an oxazolidone group, a urethane group, and an acrylate group, and having a molecular weight of 500 kg / kmol or more, and

(B) reactive diluents.

The invention further relates to a radiation curable coating composition comprising a radiation curable oligomer, a reactive diluent, and a photoinitiator in an amount such that when the composition cures, the following properties (i) and (ii) are exhibited:

(i) a cure rate of less than about 0.17 J / cm 2 (measured by dose-modulus test) or a cure rate of less than about 0.11 seconds (time required for G 'to reach 2 x 10 ⁴ Pa) Measured by real-time DMA),

(ii) dry adhesion of at least about 250 g / in.

Compounds containing an oxazolidone group, a urethane group and an acrylate group and having a molecular weight of 500 kg / kmol or more are also referred to as oxazolidone group-containing compounds.

Surprisingly, the radiation curable coating compositions of the invention when applied and cured to optical glass fibers as a coating material have very good adhesion compared to known compositions. In addition, the radiation curable coating compositions according to the invention exhibit very fast cure rates compared to known compositions.

The compositions of the present invention may be used as colored or uncolored optical fiber single protective coatings, first (or inner first) coatings, second (or outer first) coatings, or related optical fiber protective materials, such as matrix or bundling materials. It is preferred to be designed for use. The optical fiber coatings have their own unique performance requirements, distinguishing them from conventional applications.

In addition, the compounds according to the invention and the resin compositions according to the invention are suitable for optical medium adhesives and lacquers, superconductor coatings, adhesives for electronics, sealants and potting compounds, lenses and lenses. It can be designed for use as a coating or as a hardcoat. For example, the resin composition can be used as a DVD adhesive in which improved adhesion is obtained by bonding metal layers.

The present invention also relates to certain methods of preparing oxazolidone group containing compounds and to a novel group of oxazolidone group containing compounds.

The radiation curable coating composition according to the invention preferably comprises (C) and (D) in addition to components (A) and (B):

(C) one or more photoinitiators, and / or

(D) at least one additive.

Preferably, the radiation curable coating composition according to the present invention (when measured by dose-modulus test) is about 0.16 J / cm 2 or less, more preferably about 0.14 J / cm 2 or less, even more preferably about 0.12 J / cm 2 Or less preferably about 0.10 J / cm 2 or less, most preferably about 0.08 J / cm 2 or less.

Preferably, the radiation curable coating composition according to the invention is less than about 0.10 seconds, more preferably less than about 0.09 seconds, even more (as measured by real time DMA as the time required for G 'to reach 2 x 10 ⁴ Pa) It preferably has a cure rate of about 0.08 seconds or less, particularly preferably about 0.06 seconds or less.

Preferably, the dry adhesion of the radiation curable coating composition according to the invention is at least about 300 g / in, more preferably at least about 350 g / in, even more preferably at least about 400 g / in, particularly preferably at least about It has a thickness of 450 g / in or more, and most preferably, the adhesion of the coating material to the glass is so strong that the coating film breaks before delamination occurs.

(A) Heterocyclic group containing compound and oxazolidone group containing compound

According to one embodiment of the present invention, a preferred important factor for obtaining an improved radiation curable composition according to the present invention is the presence of a heterocyclic group containing compound in the composition, wherein the heterocyclic group is at least 2.5 dibi, more preferably It has a Boltzmann average dipole moment of at least 3.0 divi, even more preferably at least 3.5 divi, particularly preferably at least 4.0 divi, and most preferably at least 4.5 divi.

Examples of heterocyclic groups having high dipole moments and falling within the scope of the present invention include 5- or 6-membered ring phosphates, 5- or 6-membered ring phosphites, 4-membered ring lactones, 5-membered ring lactones, 6-membered ring lactone, 5-membered ring carbonate, 6-membered ring carbonate, 5-membered ring sulfate, 6-membered ring sulfate, 5-membered ring sulfoxide, 6-membered ring sulfoxide, 6- Components having functional groups selected from the group consisting of atomic ring amides, 5-membered ring urethanes, 6-membered ring urethanes, 7-membered ring urethanes, 5-membered ring ureas, 6-membered ring ureas and 7-membered ring ureas have. Urethane groups in the molecule, and 5-membered ring phosphate, 6-membered ring phosphate, 5-membered ring phosphite, 6-membered ring phosphite tetracyclic lactone, 5-membered ring lactone, 6-membered ring lactone, 5-atomic Cyclic carbonates, 6-membered ring carbonates, 5-membered ring sulfate, 6-membered ring sulfate, 5-membered sulfoxide, 6-membered ring sulfoxide, 5-membered ring amide, 6-membered ring amide, 7 Particular preference is given to cyclic amides, 5-membered ring urethanes, 6-membered ring urethanes, 7-membered ring urethanes, 5-membered ring ureas, 6-membered ring ureas, 7-membered ring ureas.

Also highly reactive, preferred components include carbonate functionality in the molecule, 5-membered ring phosphate, 6-membered ring phosphate, 5-membered ring phosphite, 6-membered ring phosphite, 4-membered ring lactone, 5- Atomic ring lactones, 6-membered ring lactones, 5-membered ring carbonates, 6-membered ring carbonates, 5-membered ring sulfates or sulfites, 6-membered ring sulfates or sulfites, 5-membered ring sulfates , 6-membered ring sulfite, 5-membered ring sulfoxide, 6-membered ring sulfoxide, 5-membered ring amide, 5-membered ring imide, 6-membered ring amide, 7-membered ring amide, 5-atomic Ring imides, 6-membered ring imides, 5-membered ring thiimides, 6-membered ring thiimides, 5-membered ring urethanes, 6-membered ring urethanes, 7-membered ring urethanes, 5-membered ring ureas, 6 -With atomic ring urea and with 7-membered ring urea Luer are binary components having both a functional group selected from the.

Preferred compositions according to the invention are radiation curable coating compositions, wherein the heterocyclic group is an oxazolidone group containing compound.

Very suitable compositions according to the invention are radiation curable coating compositions, wherein the compound comprising an oxazolidone group, a urethane group and a (meth) acrylate group is a compound represented by the following formula (1) or a compound represented by the following formula (2).

(In Formula 1,

P is an oligomer or polymer backbone linked with either the 4th or 5th position of oxazolidone,

n is 2 to 40,

R is H, C ₁ -C ₅ alkyl,

R ₁ is C ₁ -C ₃₀ alkyl, cycloalkyl, aryl or alkylaryl,

R ₂ is C ₁ -C ₁₂ alkyl, cycloalkyl, aryl, alkylaryl, alkoxy alkyl or alkoxy aryl)

(In Formula 2,

P is an oligomer or polymer backbone,

n is 2 to 40,

R is H, C ₁ -C ₅ alkyl,

R ₁ is C ₁ -C ₃₀ alkyl, cycloalkyl, aryl or alkylaryl,

R ₂ is C ₁ -C ₁₂ alkyl, cycloalkyl, aryl, alkylaryl, alkoxy alkyl or alkoxy aryl, linked to one of the fourth or fifth positions of oxazolidone)

Preferably, n is 2 to 10, more preferably n is 2. Preferably, R is H or CH ₃ . Preferably R ₁ is C ₂ -C ₂₀ alkyl, cycloalkyl, aryl or arylalkyl, more preferably R ₁ is cycloalkyl, most preferably R ₁ is cyclohexyl. In a further preferred embodiment, R ₁ is represented by the formula (I):

Preferably R ₂ is methyl, ethyl, 1-propyl, 2-propyl, butyl or ethoxyethyl. In another further preferred embodiment, R ₁ is represented by the formula (I) above and R ₂ is ethyl because the composition comprising the compound exhibits excellent processability.

Suitable polymers and oligomers P are, for example, polymers and oligomers obtained by addition reactions or condensation reactions.

Although the terms oligomer and polymer are used herein, there is no clear distinction between oligomer and polymer. Oligomers tend to have a low molecular weight range, and polymers tend to have a high molecular weight range. Thereafter, the terms "oligomer" and "polymer" are used interchangeably.

The polymers and oligomers can be, for example, linear, branched, and have a honeycomb structure, a star structure and a ladder structure. Also useful are dendrimers and hyperbranched polymers.

Suitable additive polymers and oligomers P are for example, such as (meth) acrylates, acrylamides, styrenes, ethylene, propylene, maleic acid, cyanoacrylates, vinyl acetates, vinyl ethers, vinyl chlorides, vinylsilanes and mixtures thereof Polymers and oligomers derived from monomers.

Suitable condensation polymers and oligomers P include, for example, polyesters, polylactones, polyamides, polyesteramides, polyethers, polyesterethers, polyurethanes and polyurethane-ureas.

Suitable linear polymers and oligomers P include polyethers derived from diols, polyethylene, poly-MMA, polyesters derived from diols, difunctional acids and / or mono-hydroxy acids. do.

Suitable branched polymers and oligomers P are, for example, polyethers comprising at least one trifunctional alcohol unit, at least one trifunctional or tetrafunctional alcohol unit and / or one trifunctional / 4 functional acid It includes a polyester containing a unit.

Suitable dendrimers are described, for example, in EP-A-575596, EP-A-707611, EP-A-741756, EP-A-672703, Angew. Chem. Int. Ed. Eng. 1994, 33, 2413, Angew. Chem. Int Ed. Eng. 1990, 29, 138, Angew. Chem. Int. Ed. Eng. 1993, 32, 1308, and Angew. Chem. Int. Ed. Eng. 1992, 31, 1200.

Suitable hyperbranched polymers include, for example, condensation polymers containing β-hydroxyalkylamide groups and having a weight average molecular weight of at least 800 g / mol.

In the case of compounds represented by the formula (1), P is preferably derived from epoxy functional, more preferably glycidyl functional polymers or oligomers. Epoxy functional polymers or oligomers may be obtainable, for example, by epoxidation of the remaining unsaturated of the additive polymer or oligomer.

Examples of glycidyl functional polymers or oligomers include polytetrahydrofuran (THF) diglycidyl ether, polypropylene glycol diglycidyl ether, ethoxylated bisphenol A diglycidyl ether and propoxylated bisphenol A di Glycidyl ether.

Preferably, the glycidyl functional polymers and oligomers are replacements thereof derived from polyols.

In the case of the compound represented by the formula (2), P is preferably derived directly from the polyol.

Examples of suitable polyols are polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, acrylic polyols, and other polyols. The polyols can be used individually or in combination of two or more. There is no particular limitation on the method of polymerization of structural units in the polyol. Any random polymerization, block polymerization, or graft polymerization is acceptable.

Given as examples of polyether polyols are polyethylene glycol, polypropylene glycol, polypropylene glycol-ethylene glycol copolymers, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, and two or more ions- There is a polyether diol obtained by ring-opening copolymerization of polymerizable ring compounds. Here, given as examples of ion-polymerizable ring compounds are ring ethers such as ethylene oxide, isobutene oxide, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, Tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, isoprene monooxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether and glyc Cyclic ethers such as cydyl benzoate. Specific examples of combinations of two or more ion-polymerizable ring compounds include combinations for preparing binary copolymers such as tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, and Tetrahydrofuran and ethylene oxide; And blends for preparing ternary copolymers such as tetrahydrofuran, 2-methyltetrahydrofuran and ethylene oxide blends, blends of tetrahydrofuran, butene-1-oxide and ethylene oxide, and the like. The ring-opening copolymer of the ion-polymerizable ring compound may be a random copolymer or a block copolymer.

Examples of the polyether polyol include PTMG 1000, PTMG 2000 (manufactured by Mitsubishi Chemical Corp.), PEG # 1000 (manufactured by Nippon Oil and Fats Co., Ltd.), PTG650 (SN), PTG1000 (SN), PTG2000 (SN), PTG3000, PTGL1000, PTGL2000 (manufactured by Hodogaya Chemical Co., Ltd.), PEG400, PEG600, PEG1000, PEG1500, PEG2000, PEG4000, PEG6000 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and Pluronics , Manufactured by BASF).

Polyester diols obtained by reacting polyhydric alcohols with polyacids are given as examples of polyester polyols. Examples of polyhydric alcohols include ethylene glycol, polyethylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl- 1,8-octanediol and the like can be given. As examples of polyacids, phthalic acid, dimer acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid and the like can be given.

The polyester polyol compound is MPD / IPA500, MPD / IPA1000, MPD / IPA2000, MPD / TPA500, MPD / TPA1000, MPD / TPA2000, Kurapol A-1010, A-2010, PNA-2000, PNOA-1010 And PNOA-2010 (manufactured by Kuraray Co., Ltd.).

Examples of polycarbonate polyols include polycarbonates of polytetrahydrofuran, poly (hexanediol carbonate), poly (nonanediol carbonate), poly (3-methyl-1,5-pentamethylene carbonate Carbonates), and the like.

As a commercially available product of the polycarbonate polyol, DN-980, DN-981 (manufactured by Nippon Polyurethane Industry Co., Ltd.), Preplast 3196, 3190, 2033 (manufactured by Unichema), PNOC-2000 , PNOC-1000 (manufactured by Kuraray Co., Ltd.), PLACCEL CD220, CD210, CD208, CD205 (manufactured by Daicel Chemical Industries, Ltd.), PC-THF-CD (manufactured by BASF), and the like.

Polycaprolactone diols obtained by reacting ε-caprolactone and diol compounds are given as examples of polycaprolactone polyols having a melting point of at least 0 ° C. Here, examples of diol compounds are given as ethylene glycol, polyethylene glycol, polypropylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentyl Glycols, 1,4-cyclohexanedimethanol, 1,4-butanediol and the like.

Commercially available products of the polycaprolactone polyol include PLACCEL 240, 230, 230ST, 220, 220ST, 220NP1, 212, 210, 220N, 210N, L230AL, L220AL, L220PL, L220PM, L212AL (manufactured by Daicel Chemical Industries, Ltd.), Rauccarb 107 (manufactured by Enichem) and the like.

Examples of other polyols include ethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, polyoxyethylene bisphenol A ether, polyoxypropylene bisphenol A ether, polyoxyethylene bisphenol F ether, Polyoxypropylene bisphenol F ether and the like can be given.

As said other polyols, those having an alkylene oxide structure in the molecule are particularly preferred polyether polyols. In particular, polyol containing polytetramethylene glycol and copolymer glycol of butylene oxide and ethylene oxide are particularly preferable.

The reduced number average molecular weight derived from the hydroxyl value of the polyol is generally about 50 to about 15,000, preferably about 1,000 to about 8,000.

Given as examples of polyisocyanates used for oxazolidone group-containing compounds are 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene di Isocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane Diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexyl isocyanate), 2, 2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanato-ethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane di Socia Sites, and the like hydrogenation keusil ylene diisocyanate, tetramethyl keusil ylene diisocyanate, lysine isocyanate. The polyisocyanate compounds can be used individually or in combination of two or more. Preferred polyisocyanates are 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexyl isocyanate) and hydrogenated diphenylmethane diisocyanate. A composition having very good processability is obtained with the isocyanate.

Examples of hydroxyl group-containing (meth) acrylates used in oligomers include (meth) acrylates derived from (meth) acrylic acid and epoxy, and (meth) acrylates including alkylene oxides, more particularly 2- Hydroxy ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxy-3-oxyphenyl (meth) acrylate. An acrylate functional group is more preferable than methacrylate. Further examples are given in US-3,979,406, which is incorporated herein by reference.

In the case of compounds according to formula (2), hydroxy (meth) acrylates are capable of conversion to epoxy (meth) acrylates by epoxidizing the hydroxyl groups of hydroxy (meth) acrylates.

In addition, P may be P 'including two or more P blocks. The blocks may be the same or different.

The number average molecular weight of the heterocyclic group (preferably oxazolidone) containing compound used in the composition of the present invention is in the range of about 800 to about 20,000, more preferably 1,200 to 12,000, more preferably about 2,200 to about 8,000 Is preferred. Particularly preferred for the first coating material are heterocyclic (preferably oxazolidone) containing compounds or oligomers having a number average molecular weight of 2,200 to 5,500, more preferably 2,500 to 4,500, even more preferably 2,700 to 4,000. .

The heterocyclic group (preferably oxazolidone) containing compound is from about 10% to about 95% by weight, preferably about 20% by weight, based on the total weight of the total amount of the coating composition of (A) and (B) It is suitable to use in an amount of from about 80% by weight. When the composition is used as coating material for optical fibers, the excellent flexibility and long-term reliability of the cured coating material in the range of about 20% to about 80% by weight, more preferably about 30% to about 70% by weight It is particularly desirable to ensure excellent coatability as well.

In addition to the heterocyclic group (preferably oxazolidone group) containing compound (A), it is also possible for the composition according to the invention to comprise an oligomer (E), said oligomer (E) being a urethane (meth) acrylate oligomer and / Or in reaction of another oligomer such as polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, (meth) acryloyloxy group, (meth) acrylic acid It is selected from the group consisting of reactive polymers obtained by the copolymer, copolymers of glycidyl methacrylate and other polymerizable monomers, and the like. Bisphenol A-based (meth) acrylate oligomers such as alkoxylated bisphenol-A-di (meth) acrylate and diglycidyl-bisphenol-A-di (meth) acrylate are particularly preferred. Preferably in the radiation curable coating compositions according to the invention, the ratio of component (A) / (E) is at least 1, more preferably at least 2, particularly preferably at least 8.

In addition to the components disclosed above, additional curable oligomers or polymers (E) may be added to the curable coating compositions of the present invention to the extent that they do not adversely affect the properties of the liquid curable resin composition.

Preferred oligomers (E) are polyether-based (meth) acrylate oligomers, polycarbonate (meth) acrylate oligomers, polyester (meth) acrylate oligomers, alkyd (meth) acrylate oligomers and acrylated acrylic oligomers. More preferred are urethane-containing oligomers. Even more preferred are urethane (meth) acrylate oligomers using a mixture of polyether urethane (meth) acrylate oligomers and the above polyols, with aliphatic polyether urethane (meth) acrylate oligomers being particularly preferred. The term "aliphatic" refers to the fully aliphatic polyisocyanate used. However, also urethane free (meth) acrylate oligomers such as urethane free (meth) acrylate acrylic oligomers, urethane free polyester (meth) acrylate oligomers, and urethane free alkyd (meth) acrylate oligomers are also desirable.

The present invention also relates to a preferred method for producing an oxazolidone group-containing compound, and to a preferred method for producing a resin composition comprising the compound.

Processes for the preparation of compounds according to formula (2) are known from US-3,979,406. However, the resin composition obtained by the method described in US-3,979,406 presents a disadvantage of very high viscosity. Thus, the resin composition is inadequate for preparing the curable coating composition according to the present invention.

In the process according to the invention, a reaction step of introducing a (meth) acrylate group into the oxazolidone group-containing compound is carried out in the presence of an antioxidant.

In this method, the resin composition is obtained with a lower viscosity, and therefore the composition is very suitable for preparing the composition according to the present invention.

Preferably, the method according to the invention is a method for producing a resin composition comprising the compound comprising an oxazolidone group and a (meth) acrylate group, more preferably a urethane group.

The oxazolidone group-containing compound prepared according to the method of the present invention has an Mw / Mn of about 10 or less, more preferably about 8 or less, even more preferably about 5 or less, most preferably about 3.5 or less (wherein Mw Is a weight average molecular weight, and Mn is a number average molecular weight), preferably having polydispersity D characterized by the ratio.

The gel fraction of the resin composition comprising the oxazolidone-containing compound prepared according to the method of the present invention is about 5% or less, more preferably about 4% or less, and particularly preferably about 3% or less desirable. The gel fraction filters out the insoluble, gelled fraction of the resin composition and measures the weight of the fraction.

The method according to the present invention is to prepare a resin composition comprising an oxazolidone-containing compound represented by the formula (1) or (2), or an oxazolidone (meth) acrylate difunctional monomer represented by the following formula (3) It is especially suitable for:

(In Chemical Formula 3,

R is H, C ₁ -C ₅ alkyl,

R ₁ is C ₁ -C ₃₀ alkyl, cycloalkyl, aryl or alkylaryl, and

R ₂ is C ₁ -C ₁₂ alkyl, cycloalkyl, aryl, alkylaryl, alkoxy alkyl or alkoxy aryl, linked to one of the fourth or fifth positions of oxazolidone)

Suitable antioxidants can be, for example, metal based, amine based, phosphine based, sulfide based or phenol based.

Examples of metal-based antioxidants are, for example, zinc dialkyl thiocarbamate, nickel dialkyl thiocarbamate, zinc-2-mercapto-toluimidazole, and examples of amine antioxidants are, for example, N , N-diphenyl-p-phenylene diamine, dioctyl diphenyl amine, N, N'-di-sec-butyl-p-phenylene diamine, naphthyl phenyl amine.

Examples of phosphine-based antioxidants include, for example, trisnonylphenyl phosphite, trilauryl phosphite, di-iso octyl phosphite, di-isodecyl phenyl phosphite, triphenyl phosphite, tris (dipropylene glycol) phosphite , Diphenyl phosphite, bis (2,4-di-t-butyl-phenyl) pentaerythritol diphosphite.

Examples of sulfide-based antioxidants are, for example, dilauryl thiodipropionate, di octadecyl disulfide.

Examples of phenolic antioxidants are, for example, hydroquinone, methyl hydroquinone, 2,6-dibutyl hydroquinone, diamyl hydroquinone, 2-t-butyl-4-methyl phenol, butylated hydroxyanisol, 2,6-di -t-butyl-4-methyl phenol, 2,6-di-t-butyl-4-dimethyl aminomethyl phenol, 2,6-diphenyl-4-octadecyl cyclooxy phenol, diethyl- (3,5 Di-t-butyl-4-hydroxy benzyl phosphate, propyl gallate, 4-methyl-2,6-bis (2-phenylethenyl) phenol, 2,6-di-t-butyl phenol, bisphenol A have.

Phenolic antioxidants are preferred. Preferred phenolic antioxidants include di-t-butyl hydroxy toluene and 2,6-dibutyl-hydroquinone.

Antioxidants are used, for example, in amounts of 500 ppm to 10,000 ppm, preferably 800 ppm to 2000 ppm.

A further improved process according to the invention is that during the reaction step of introducing (meth) acrylate groups into the oxazolidone group-containing compound, oxygen or an oxygen-containing gas mixture, preferably air, is brought into the reaction mixture and consequently through the reaction mixture. Obtained when derived. The resin composition obtained by the above method is more suitable for the preparation of the composition according to the present invention.

Preferably, dry oxygen or a dry oxygen containing gas mixture is used. Preferably the oxygen or gas mixture comprises at most 0.1% by weight, more preferably at most 0.03% by weight and even more preferably at most 0.01% by weight of water, in particular the water content being very small as possible.

The amount of oxygen used is the amount of oxygen dissolved in the reaction mixture in an amount equal to or more than oxygen (based on moles).

In the method for producing the oxazolidone group-containing compound according to the present invention, the subsequent reaction step is preferably carried out in the order of introducing (meth) acrylate groups into the compound during the last reaction step. The coating composition obtained in this way is more suitable for the preparation of the composition according to the invention.

The compound represented by the formula (1) is preferably prepared by first reacting a polyol with an epoxy group-forming compound (eg, epichlorohydrin). In this method, glycidyl functional polyols are formed. Thereafter, the obtained compound is reacted with diisocyanate in the presence of an oxazolidone forming catalyst. Finally, the compound comprising the free isocyanate group obtained above is reacted with hydroxy (meth) acrylate in the presence of a urethane formation catalyst. Methods of performing each individual step are known to those of ordinary skill in the art.

The compound of the formula (2) comprises the first step of reacting a polyol and a diisocyanate in the presence of a urethane forming catalyst and an epoxy functional (meth) acrylate, preferably glyco, obtained in the presence of an oxazolidone forming catalyst. It is preferred that the cylyl functional (meth) acrylate is prepared by the second step in which it reacts.

The compound of formula (3) is preferably prepared by reacting an epoxy functional (meth) acrylate, preferably glycidyl functional (meth) acrylate with diisocyanate in the presence of an oxazolidone forming catalyst.

Examples of oxazolidone forming catalysts include tertiary amines such as dimethyl benzylamine, dimethylcyclohexyl amine, tetra methyl ethylene diamine, N-methyl morpholine, 1,8-diaza bicyclo- (5,4,0)- 7-undecene, 1,4-diaza bicyclo (2,2,2) octane, pyridine, quinoline imidazole or Lewis acids such as quaternary ammonium salts such as tetra methyl ammonium bromide or tetra ethyl ammonium ioda Ids, quaternary phosphonium salts such as tetrabutyl phosphonium bromide. Preferably, metalic Lewis acids are used, such as quaternary antimonium salts such as tributyl antimonium diiodide, tetraethyl antimonium bromide, metal alkoxylates such as lithium butoxide, sodium butoxide, magnesium phenoxide or Aluminum phenoxides, halides of alkalis, alkali metals, and Group 3 metals of the periodic table, for example lithium chloride, lithium bromide, magnesium chloride, iron chloride, aluminum chloride or zinc chloride, tin salts and complexes, for example Trialkyltin halide, tin chloride, tin octoate, dioctyl tin oxide, DBTDL or organoalkyl or organic alkoxylates such as diethyl zinc trimethyl alumina, or zinc dicarboxylate and mixtures thereof.

According to a more preferred embodiment, the Lewis acid has a Lewisbase such as phosphine, phosphine oxide and phosphate such as triphenyl phosphine, triphenyl phosphine oxide, tributyl phosphine oxide, tris (dimethyl amino) Phosphine oxide or tris (2-ethylhexyl) phosphine oxide, triethyl phosphate. As Lewis bases also tertiary amines can be applied. Lewis bases and Lewis acids can be mixtures of Lewis bases and Lewis acids, respectively.

The reaction is carried out, for example, at a temperature of 100 ° C. to 150 ° C., and 1 atmosphere. It is preferable not to use a solvent during the reaction.

Preferably, the reaction step of forming the oxazolidone group is carried out in the presence of an antioxidant. In this method, a coating composition having high transparency is obtained. Examples of antioxidants are shown above. It is preferable to use a phosphine antioxidant in the reaction step.

In the urethane group forming reaction step, urethane forming catalysts such as copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyl tin dilaurate, triethylamine, and triethylenediamine-2-methyltri Ethyleneamine is generally used in amounts of about 0.01% to about 1% by weight based on the total amount of reactants. The reaction is carried out at a temperature of about 10 ° C to about 90 ° C, and preferably about 30 ° C to about 80 ° C.

The invention also relates to a resin composition obtainable by the process according to the invention.

The invention also relates to a compound represented by formula (1).

The compound represented by the formula (1) has proved to be very advantageous for use in the composition according to the invention because the processability of the composition is very good due to its advantageous low viscosity, while retaining further good properties of the composition.

(B) reactive diluent

Suitable reactive diluents are listed below.

A polymerizable vinyl monomer such as a polymerizable monofunctional vinyl monomer containing one polymerizable vinyl group in a molecule, and a polymerizable polyfunctional vinyl monomer containing two or more polymerizable vinyl groups in a molecule are liquid curable resin compositions of the present invention. Can be added to.

Specific examples of the polymerizable monofunctional vinyl monomers include vinyl monomers such as N-vinyl pyrrolidone, N-vinyl caprolactam, vinyl imidazole, and vinyl pyridine; (Meth) acrylate-containing alicyclic structures such as isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclophene Tenyl (meth) acrylate, and cyclohexyl (meth) acrylate; Benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloyl morpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy Butyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) Acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate , Dodecyl (meth) Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene Glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylic Ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, diacetone (meth) acrylamide, isobutoxy methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate , 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethyl amino propyl (meth) acrylamide, hydroxy butyl vinyl ether, Usyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, an acrylate monomer represented by the following general formula (II).

(In Formula II,

R ⁷ is a hydrogen atom or a methyl group,

R ⁸ is an alkylene group having from 2 to 6, preferably from 2 to 4 carbon atoms,

R ⁹ is a hydrogen atom or an organic group containing 1 to 12 carbon atoms or an aromatic ring,

r is an integer from 0 to 12, preferably 1 to 8)

Given as examples of polymerizable polyfunctional vinyl monomers are the following (meth) acrylate compounds: trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth ) Acrylate, trimethylolpropanetrioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth ) Di (meth) of diol which added compound of ethylene oxide or propylene oxide to acrylate, bis (hydroxymethyl) tricyclodecane di (meth) acrylate, and bisphenol A Epoxy obtained by adding di (meth) acrylate of diol to which ethylene oxide or propylene oxide compound is added to acrylate, hydrogenated bisphenol A and (meth) acrylate to diglycidyl ether of bisphenol A ) Acrylate, diacrylate of polyoxyalkylene bisphenol A, and triethylene glycol divinyl ether.

Preferred reactive diluents are alkoxylated alkyl substituted phenol (meth) acrylates such as ethoxylated nonyl phenol (meth) acrylate, vinyl monomers such as vinyl caprolactam, isodecyl (meth) acrylate, and alkoxylated bisphenol A di ( Meth) acrylates such as ethoxylated bisphenol A diacrylate.

(C) photoinitiator

The liquid curable resin composition of the present invention can be cured with radiation, and preferably one or more photo-polymerization initiators are used. In addition, photosensitizers or synergists may be added as needed. Given as examples of photo-polymerization initiators are 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenyl Amines, carbazoles, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michaeller's ketone, benzoin propyl ether, Benzoin ethyl ether, benzyl methyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one , Thioxanthone, diethyl thioxanthone, 2-isopropyl thioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane- 1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,4 , 6-trimethylbenzoyl) -phenylphosphine oxide and the like. Mixtures of such photo-polymerization initiators may also be used.

Examples of commercially available products of photo-polymerization initiators include IRGACURE 184, 369, 651, 500, 907, 1700, 1750, 1850, 819, CG24-61, Darocur 1116, 1173 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Lucirin LR8728 (manufactured by BASF), Ebecryl P36 (manufactured by UCB), and the like.

Given as examples of photosensitizers or synergists are triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate , Isoamyl 4-dimethylaminobenzoate and the like. Commercially available products for photosensitizers include, for example, ebecryl P102, 103, 104 and 105 (manufactured by UCB). The use of synergist mixtures is also possible.

The amount of polymerization initiator used here is preferably in the range of 0.1% to 10% by weight, more preferably 0.5% to 7% by weight, based on the total amount of the resin composition components.

In addition to the components described above, other curable oligomers or polymers may be added to the liquid resin composition of the present invention to an extent that does not adversely affect the properties of the liquid curable resin composition.

(D) additive

The amine compound can be added to the liquid curable resin composition of the present invention to prevent generation of hydrogen gas causing transmission loss in the optical fiber. As examples of the amines that can be used here, diallylamine, diisopropylamine, diethylamine, diethylhexylamine and the like can be given.

In addition to the components described above, various additives such as antioxidants, UV absorbers, light stabilizers, silane coupling agents, coating surface improvers, heat polymerization inhibitors, leveling agents ( Leveling agents, surfactants, colorants, preservatives, plasticizers, lubricants, solvents, fillers, aging preventives, and wettability improvers can be used in the liquid curable resin compositions of the present invention if needed. have.

Examples of silane binders include aminopropyltriethoxysilane, mercaptopropyltrimethoxy-silane and methacryloxypropyltrimethoxysilane, and commercially available products such as SH 6062, SH6030 (Toray-Dow Corning silicone Co., Ltd .) And KBE903, KBE603, KBE403 (manufactured by Shin-Etsu Chemical Co., Ltd.).

The description of the radiation curable composition may also be applied to the colored composition, and may be a single colored, first colored second or second external first composition, ink composition, or colored matrix or bundling material. The colorant may be a pigment or a dye. The pigment may be any pigment suitable for use in pigmented colored optical fiber coatings. Preferably, the pigment is resistant to UV-radiation and is in the form of small particles.

Pigments are described, for example, in Ullman's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. Conventional or organic pigments as described in A22, VCH Publishers (1993), pages 154-155. The pigment may for example be selected based on the second ink coating or matrix material on which the composition is colored. Ink coatings are usually more colored.

General classifications of suitable colorants include, among others, inorganic white pigments; Black pigments; Iron oxide; Chromium oxide green; Iron blue and chrome painted; Violet pigments; Ultramarine pigments; Blue, green, yellow and brown metal blends; Lead chromate and lead molybdate; Cadmium pigments; Titanium pigments; Pearlescent pigments; Metallic pigments; Monoazo pigments, diazo pigments; Diazo condensation pigments; Quinacridone pigments, dioxazine violet pigments; Bat pigments; Perylene pigments; Thioindigo pigments; Phthalocyanine pigments; And tetrachloroindolinone; Azo dyes; Anthraquinone dyes; Xanthone dyes; And azine dyes. Fluorescent pigments may also be used.

Preferably, the pigment has an average particle size of about 1 μm or less. The particle size of commercial pigments can be made smaller by grinding if necessary. The pigment is preferably present in an amount of about 1% to about 10% by weight, more preferably about 3% to about 8% by weight.

Instead of pigments, dyes may also be used if they are effectively color stable. Reactive dyes are particularly preferred. Suitable dyes include polymethine dyes, di and triarylmethine dyes, aza analogs of diarylmethine dyes, aza (18) annenlenes (or natural dyes), nitro and nitroso dyes, aza dyes, anthraquinone dyes, and sulfur Dyes. Such dyes are well known in the art.

All such additives may be added to the compositions according to the invention in conventional amounts for the additives when used in special applications such as optical fiber coatings.

Physical properties

The viscosity of the liquid curable resin composition of the present invention generally ranges from about 200 cP to about 20,000 cP, preferably from about 2,000 cP to about 15,000 cP.

The radiation curable compositions of the present invention may be formulated for use as a single coating, first coating, second coating, matrix material or bundling material (all of which may or may not be colored), or as ink. . In particular, the radiation-curable compositions of the invention can be formulated so that after curing the composition has a modulus of 0.1 MPa or less, and a modulus of 2,000 MPa or more. Compositions having a modulus of a low range, for example 0.1 MPa to 10 MPa, preferably 0.1 MPa to 5 MPa, and more preferably 0.5 MPa to 3 MPa or less, are generally suitable as the first coating for optical fibers. In contrast, suitable compositions for the second coating, ink and matrix material have a modulus of at least 50 MPa, the second coating has a modulus of more than about 100 MPa to 1,000 MPa, and the matrix material is more particularly for soft matrix material Between about 50 MPa and about 200 MPa, and between 200 MPa and 1500 MPa for hard matrix materials. The radiation-curable composition of the present invention may be formulated so that after curing, the composition has a Tg range of -70 ° C to 30 ° C.

The glass transition temperature (Tg), measured as peak tan-delta measured by dynamic mechanical analysis (DMA), can be optimized according to the specificity of the application. The glass transition temperature is from 10 ° C. to -70 ° C., more preferably 0 ° C. or lower for compositions formulated for use as the first coating, and 10 for compositions designed for use as the second coating, ink and matrix material. The temperature may be at least 120 ° C and more preferably at least 30 ° C.

The elongation and tensile strength of the material can be optimized according to the devised standards for the particular application. In cured coatings formed from radiation-curable compositions formulated for use as internal first coatings on optical fibers, elongation-at-break is usually at least 65%, preferably at least 80%, more preferred. Preferably the elongation at break is at least 110%, more preferably at least 150%, but usually does not exceed 400%. In coatings formulated for the outer first coating, ink and matrix material, the elongation at break is usually 6% to 100%, and preferably at least 10%.

The present invention is further illustrated by experiment, but not limited thereto.

Analyze Method Description

Compounds prepared in the examples and comparative experiments were analyzed as follows:

Infrared spectroscopy (Bruker ^™ ISS 55),

To quantitatively record the carbonyl signals of NMR [Bruker 400 MHz, oxazolidone, urethane and (meth) acrylate carbonyl, spectra were recorded in deuterated chloroform and ¹³ C NMR was measured for 120 seconds. Recorded according to relaxation time],

Waters Alliance 2690 separation module, Calibration: SEC_LT4_20011010, Eluent: THF Biosolve, with Waters 2410 Refractive Index Detector (GPC) HPLC-grade, flow rate: 1.0 ml / min, column: 1 ^* PL Gel Mixed C (with guard column, 5 μm) and precolumn filter, temperature: 30 ° C. compared to polystyrene standard (Columns and detectors)]

Describe the test method and the calculation method

The radiation curable compositions prepared in Examples and Comparative Experiments were tested by the following test methods.

How to measure the cure rate

1.Measurement of curing rate by dose versus modulus measurement

In this method, the tensile modulus of the radiation curable coating composition at various dosages was measured to obtain a dosage versus modulus curve. The cure rate was defined as the dose until 95% of the final modulus value was achieved.

For each radiation curable coating composition to be tested, one drawdown (cured film) was prepared at each series of doses (J / cm 2): 0.2 J / cm 2, 0.3 J / cm 2, 0.5 J / cm 2 , 0.75 J / cm 2, 1.0 J / cm 2 and 2.0 J / cm 2.

For each drawdown, the test piece was prepared by cutting five test pieces from the center position of each drawdown. A single measurement of the film thickness was made at the center of each test piece area to be tested. The modulus of each test piece was measured at the first drawdown. The stress-strain curve was measured with an elongation of 2.5% or more. The measurement was repeated for each drawdown of the dose-modulus curve. The average modulus was then determined for each drawdown.

Least squares fit is performed with modulus versus dose data to fit the following nonlinear equation:

Dose-modulus curves were created by plotting the equations as linear and modulus values as scatter plots. Error bars representing the standard deviation of each modulus value were included whenever possible. The rate of cure of the coating is defined as "the dose at which 95% of the ultimate secant modulus is attained".

2. Determination of Cure Speed by Real-Time DMA ("RTDMA")

The basic equipment is a StressTech rheometer with UV curing attachments. The main property of UV appendages is usually replaced by a quartz plate that allows the low metal plate to transmit UV light to the following sample.

The UV source is Bluepoint 2 (manufactured by Dr. Honle Company) with an iron-doped lamp. Flexible light guides made of quartz fibers direct light from the lamp to the lower position of the sample so that the light can be directed directly to the bottom of the sample.

The size of the sample is 8 mm diameter x 0.1 mm thick and the instrument gap setting is 0.1 mm as measured by an upper tool of 8 mm diameter.

The best estimate of the UV intensity at the sample location is 105 milliwatts / cm 2 as measured by an IL 1445 radiometer (manufactured by International Light Co.). The spectral sensitivity for the detector is substantially the same as for IL390B. The intensity corresponds to about 1 J / cm 2 at 9.5 seconds. After placing the sample, setting the gap, close the door of the oven and add nitrogen gas to the oven for 15 minutes before curing the sample. The measurement is carried out at 23 ° C.

At the beginning of the experiment (0 seconds), a 10 Hz oscillation is applied to the liquid sample in the gap. Data collection begins at 1 second. In experiment 2 seconds, the software sends a relay signal to open the shutter of Bluepoint 2.

Relay combinations are solid-state relays and subsequent mechanical relays. In the latter, when the contact is closed, the shutter opens. The delay time of the relay-shutter coupling was measured and evaluated to 0.035 seconds. The shutter is set to open six seconds after receiving a signal to open. 360 data points are collected for 5 seconds during which data points are collected, providing 72 data points per second.

The horizontal axis is time and the vertical axis is plotted G 'and G "on a log scale of 100 Pa to 10 ⁶ Pa in a graph with phase angle.

The time shown in the graph for G 'reaching 2 × 10 ⁴ Pa is the time after the experiment was started. In order to obtain the time after the UV light began to illuminate the sample, 2.035 seconds were subtracted from the "raw" time to obtain the true time. Stress (Pa) versus time (in seconds) in the test RTDMA polynomial: stress ^{(t) = 100 + 200t 2} - follows a 13t ^3. Three squares are conducted per sample.

How to measure dry adhesion

Adhesion is measured by curing a film (thickness is 150 microns) on a glass plate at a dosage of 1 J / cm 2 under nitrogen using a Fusion ^™ F450 D bulb.

Dry adhesion of the coating samples was tested by using a universal testing instrument, Instron Model 4201 or equivalent, equipped with appropriate data systems and application software. Two drawdowns (film cured on glass plates) were prepared per material to be tested. Cured membranes were conditioned at 23 ° C. ± 2 ° C. and 50 ± 5% relative humidity. Four test pieces were cut from each drawdown. In order to effectively minimize small sample defects, the test pieces were cut parallel to the direction in which the drawdown of the cured film was made. A thin layer of talc can be applied to the first and third strips on each drawdown using a cotton-tipped applicator or equivalent to reduce blocking during the adhesion test. .

Load cells and pneumatic action grips were installed in Instron. The crosshead speed on the Instron test apparatus was set to 10.00 inches / minute. A binder clip is attached to the length of the braided nylon string, which is run through the pulley at the coefficient of the friction test device, and the endless wire is clamped to the upper jaw of the instron test device. . The air pressure for the pneumatic grip was turned to 20 psi.

The end of the first strip is peeled off from one glass plate of about 1 inch. The plate was placed on a COF support table with the peeled-back end of the test specimen away from the pulley. A binder clip was attached to the peeled end of the test piece. Pull the plate to tension the braided nylon strap until the load on the instron is positive. The test lasted until the mean force value became relatively constant. The test was repeated with four test pieces.

The software automatically calculates the average adhesion rate for the four specimens. The analysis was considered suspect if any replication deviated by more than 20% relative from the mean, in which case it was repeated.

Calculation of Boltzmann average dipole moment

Boltzmann average dipole moment was calculated by the following method. First, for the heterocycle considered, the setting of the initiation form was made by considering all possible bond rotations. This was done with the Discover 95 program (calculations obtained using the software program of Molecular Simulations-force field calculations were performed using the CVFF forcefield). Program), and semi-empirical calculations are performed with the MOPAC 6.0 program.

The torsional angle varies depending on the type of bond (eg, the bond between two sp ³ carbons), which corresponds to two possible asymmetric and cross structures. The number of atomic arrays thus produced depends on both its form and the number of bonds, for example in a bond like ³ sp ³ , it has 3 ⁵ = 243 atomic arrays. As a result, for some acrylates, the total number of atomic arrangements is thousands.

All of these atomic arrays are then minimized at the AM1 level using MOPAC 6.0 as the convergence standard at the maximum level (GNORM) set to 0.05. The structure obtained is then aligned by energy, and only the unique structure having a formation heat different from 3 kcal / mol or less from the heat of formation of the spherical minimum structure is preserved. Whether the structure is unique or not, it is determined by comparing their heat of formation with their dipole moments in the following manner. First, the structure is considered equal if the heat of formation differs by 0.01 kcal / mol or less. Nevertheless, structures considered to be identical on the basis of energy standards are considered unique if their dipole moments differ by more than 0.2 dibyes.

If determined to be a unique structure, the Boltzmann weight dipole moment is consequently evaluated by the following equation:

(In Equation 4,

D _j is the dipole moment of coordinate j,

△ H _j is the difference between the heat of formation of the conformation j formed rectangle column and a minimum conformation,

T is the absolute temperature

R is the Boltzmann constant,

p _j is the probability of finding the molecule in the locus j at temperature T,

T is set to 298.15 K).

The sum at j proceeds in every unique structure. Classify the structure, only the unique structure is preserved, and the calculation of <D> is executed by the developed FORTRAN program.

Considering Boltzmann weight dipole moments instead of spherical minimal dipole moments, the advantage is that the former must take into account the fact that several positions are accessible at T. It is evident that the value of <D> is significantly different from the spherical minimum dipole moment when the dipole moments of the accessible loci are significantly different. The Boltzmann weight dipole moment thus provides a more realistic description of the system.

Experimental part

The epoxy functional compounds used in the examples were purchased from EMS.

Example 1.Synthesis of oxazolidone urethane acrylate functional polytetrahydrofuran (poly THF) (Compound A)

102 g 4,4, methylene bis (cyclohexyl isocyanate) (HMDI), 1.1 g tributyl phosphine oxide, 0.3 g Lithium bromide and 0.3 g of bis (2,4-di-t-butyl-phenyl) pentaerythritol diphosphite (Ultranox 626 ^™ General Electric) were added. The mixture was stirred at 80 ° C. until all lithium bromide dissolved and then the temperature was raised to 130 ° C. 152 g of polyTHF diglycidyl ether (Mn 780) was added at 130 ° C. at a rate of ± 500 ml / hour. After the addition was complete and the reaction mixture was held at 130 ° C. for 1 hour, 0.3 g dibutyl-hydroquinone (DBH) and 0.3 g dibutyl tin dilaurate (DBTDL) were added and the reaction temperature Was reduced to 80 ° C. Dry air was purged through the reaction mixture and 45 g of 2-hydroxy ethyl acrylate (HEA) was added slowly through the reaction mixture under dry air bubbling (the rate kept the temperature below 100 ° C.). Same as the speed you let them). The addition is complete and the reaction mixture is maintained at 80 ° C. for 1 hour, after which no isocyanate is detected using IR, resulting in an oxazolidone urethane acrylate functional compound A having the following properties :

GPC: Mn = 2400 kg / kmol, D = 2.8 (D = Mw / Mn; Mw = weight average molecular weight, Mn = number average molecular weight), oxazolidone / urethane / acrylate = 2 at ¹³ C-NMR carbonyl ratio / 2/2.

Example 2. Synthesis of oxazolidone urethane acrylate functional polyTHF (Compound B)

In a 300 ml glass reactor equipped with a stirrer, a dry air inlet, a reflux condenser and a dropping funnel, 61 g of HMDI, 0.7 g of tributyl phosphine oxide, 0.2 g of lithium bromide and 0.3 g of Ultranox 626 (Trade name) was added. The mixture was stirred until the lithium bromide was all dissolved at 80 ° C. and then the temperature was raised to 130 ° C. 121 g of polyTHF diglycidyl ether (Mn 780) was added at 130 ° C. at a rate of ± 500 ml / hour. After the addition was completed, the reaction mixture was kept at 130 ° C. for 1 hour before 0.2 g dibutyl-hydroquinone (DBH) and 0.2 g DBTDL were added and the reaction temperature was reduced to 80 ° C. Dry air was purged through the reaction mixture and 18 g of HEA was slowly added under dry air bubbling through the reaction mixture (the rate is the rate that keeps the temperature below 100 ° C). After completion of the addition, isocyanate is not detected via IR after maintaining the reaction mixture at 80 ° C. for 1 hour, and an oxazolidone urethane acrylate functional compound B having the following characteristics is obtained:

GPC: Mn = 3800, D = 2.9,

Oxazolidone / urethane / acrylate at ¹³ C-NMR carbonyl ratio = 4/2/2.

Example 3 Synthesis of Oxazolidone Urethane Acrylate Functional Polypropylene Glycol PPG (Compound C)

300 g glass reactor equipped with a stirrer, dry air inlet, reflux condenser and dropping funnel with 58 g HMDI, 0.7 g tributyl phosphine oxide, 0.2 g lithium bromide and 0.2 g Ultranox 626 Put it. The mixture was stirred until the lithium bromide was all dissolved at 80 ° C. and then the temperature was raised to 130 ° C. 105 g of polypropylene glycol diglycidyl ether (Mn 710) was added at 130 ° C. at a rate of ± 500 ml / hour. After the addition was completed, the reaction mixture was kept at 130 ° C. for 1 hour before 0.2 g dibutyl-hydroquinone (DBH) and 0.2 g DBTDL were added and the reaction temperature was reduced to 80 ° C. Dry air was purged through the reaction mixture and 17 g of HEA was slowly added under dry air bubbling through the reaction mixture (the rate is the rate at which the temperature was kept below 100 ° C.). After the addition is complete, no isocyanate is detected via IR after maintaining the reaction mixture at 80 ° C. for 1 hour, and an oxazolidone urethane acrylate functional compound C is obtained having the following properties:

GPC: Mn = 3700, D = 3.0;

Oxazolidone / urethane / acrylate at ¹³ C-NMR carbonyl ratio = 4/2/2.

Example 4 Synthesis of Oxazolidone Urethane Acrylate Functional PPG (Compound D)

300 g glass reactor with stirrer, dry air inlet, reflux condenser and dropping funnel, 63 g HMDI, 0.7 g tributyl phosphine oxide, 0.2 g lithium bromide and 0.2 g Ultranox 626 (Trade name) was added. The mixture was stirred until the lithium bromide was all dissolved at 80 ° C. and then the temperature was raised to 130 ° C. 130 g of polypropylene glycol diglycidyl ether (Mn 710) was added at 130 ° C. at a rate of ± 500 ml / hour. After the addition was completed, the reaction mixture was kept at 130 ° C. for 1 hour before 0.2 g dibutyl-hydroquinone (DBH) and 0.2 g DBTDL were added and the reaction temperature was reduced to 80 ° C. Dry air was purged through the reaction mixture and 14 g of HEA was slowly added through the reaction mixture under dry air bubbling (the rate is the rate to keep the temperature below 100 ° C.). After completion of the addition, after maintaining the reaction mixture at 80 ° C. for 1 hour, no isocyanate is detected via IR and an oxazolidone urethane acrylate functional compound D having the following properties is obtained:

GPC: Mn = 5700, D = 3.2;

Oxazolidone / urethane / acrylate at ¹³ C-NMR carbonyl ratio = 6/2/2.

Example 5 Synthesis of oxazolidone urethane acrylate (Compound E) on the basis of block copolymer prepared in situ of poly THF and PPG

In a 300 ml glass reactor equipped with a stirrer, dry air inlet, reflux condenser and dropping funnel, 63 g HMDI, 0.7 g tributyl phosphine oxide, 0.2 g lithium bromide and 0.4 g Ultranox 626 Put it. The mixture was stirred until all of the lithium bromide dissolved at 80 ° C. and then the temperature was raised to 130 ° C. A mixture of 62 g polyTHF diglycidyl ether (Mn 780) and 57 g polypropylene glycol diglycidyl ether (Mn 710) was added at 130 ° C. at a rate of ± 500 ml / hour. After the addition is complete, the reaction mixture is held at 130 ° C. for 1 hour before 0.2 g dibutyl-hydroquinone (DBH) and 0.2 g DBTDL are added and the reaction temperature is reduced to 80 ° C. Dry air was purged through the reaction mixture and 18.5 g of HEA was slowly added under dry air bubbling through the reaction mixture (the rate is the rate that keeps the temperature below 100 ° C). After the addition is complete, no isocyanate is detected via IR after maintaining the reaction mixture at 80 ° C. for 1 hour, and an oxazolidone urethane acrylate functional compound F having the following properties is obtained:

GPC: Mn = 4700, D = 2.8;

Oxazolidone / urethane / acrylate at ¹³ C-NMR carbonyl ratio = 4/2/2.

Example 1 illustrates the preparation of a compound according to the invention by a method according to the invention. Examples 2-4 illustrate that the oxazolidone formation reaction can be applied in the elongation of the polymer chain. Example 5 demonstrates that the oxazolidone formation reaction can be used to form block copolymers.

Example 6 UV Curable Compositions Containing Compound B as Oligomer

As oligomer as 52.8 wt% Compound B, 9.5 wt% N-vinyl caprolactam, 8.64 wt% ethoxylated nonyl phenol acrylate [Sartomer SR504D], 9.22 wt% lauryl acrylate and reactive diluent Formulations containing 15.84 weight percent isobornyl acrylate, 3 weight percent rucerin TPO as photoinitiator, and 1 weight percent silane attachment promoter γ-mercapto propyl trimethoxy silane (OS-1 Special A-189) Prepared.

Curing rate:

The curing rate of the formulation, determined according to the dosage modulus method, is 0.06 J / cm 2. The time to reach G '2 x 10 ⁴ Pa is 0.05 seconds.

Adhesiveness:

The 150 micron membrane was cured at a dosage of 1 J / cm 2 under nitrogen using a Fusion F450 D bulb to obtain a cured membrane having the following characteristics.

Modulus:

1.5 MPa, elongation: 231%, dry adhesion to glass:> 600 g / in (membrane that breaks before delamination)

Example 7. UV Curable Compositions Containing Compound C as Oligomer

52.8 wt% Compound C as oligomer, 9.5 wt% N-vinyl caprolactam, 8.64 wt% ethoxylated nonyl phenol acrylate (Sartomer SR504D), 9.22 wt% lauryl acrylate and 15.84 wt% as reactive diluent A formulation containing isobornyl acrylate of 3 wt% Lucerine TPO as photoinitiator, and 1 wt% silane attachment promoter (A-189) was prepared.

Curing rate:

The curing rate of the formulation is 0.06 J / cm 2 according to the dosage modulus method. The time for G 'to reach 2 x 10 ⁴ Pa is 0.05 seconds.

Adhesiveness:

The 150 micron membrane was cured at a dosage of 1 J / cm 2 under nitrogen using a Fusion F450 D bulb to obtain a cured membrane having the following characteristics.

Modulus:

2.5 MPa, Elongation: 200%, Dry adhesion to glass:> 600 g / in (membrane that breaks before delamination occurs)

Example 8 UV Curable Compositions Containing Compound E as Oligomer

52.8 wt% Compound F as oligomer, 9.5 wt% N-vinyl caprolactam, 8.64 wt% ethoxylated nonyl phenol acrylate (Sartomer SR504D), 9.22 wt% lauryl acrylate and 15.84 wt% as reactive diluent A formulation containing isobornyl acrylate of 3 wt% Lucerine TPO as photoinitiator, and 1 wt% silane attachment promoter (A-189) was prepared.

Curing rate:

The curing rate of the formulation is 0.06 J / cm 2 according to the dosage modulus method. The time for G 'to reach 2 x 10 ⁴ Pa is 0.09 seconds.

Adhesiveness:

The 150 micron membrane was cured at a dosage of 1 J / cm 2 under nitrogen using a Fusion F450 D bulb to obtain a cured membrane having the following characteristics.

Modulus:

2.1 MPa, elongation: 220%, dry adhesion to glass:> 600 g / in (membrane which breaks before delamination)

Comparative Experiment A

Oligomer 1 was prepared with 2 equivalents of hydroxy ethyl acrylate, 3 equivalents of isophorone diisocyanate and 2 equivalents of pTGL 2000 (copolymer of THF and 3-methyl THF). The theoretical Mn of the polyTGL urethane acrylate oligomer is 4900.

52.8 wt% oligomer 1, 9.5 wt% N-vinyl caprolactam, 8.64 wt% ethoxylated nonyl phenol acrylate (Sartomer SR504D), 9.22 wt% lauryl acrylate and 15.84 wt% iso as a reactive diluent Formulations were prepared containing bornyl acrylate, 3 weight percent Lucerine TPO as photoinitiator, and 1 weight percent silane attachment promoter (A-189).

Curing rate:

According to the dose modulus method the curing rate of the formulation is 0.19 J / cm 2. The time for G 'to reach 2 x 10 ⁴ Pa is 0.12 seconds.

Adhesiveness:

The 150 micron membrane was cured at a dosage of 1 J / cm 2 under nitrogen using a Fusion F450 D bulb to obtain a cured membrane having the following characteristics.

Modulus:

1.4 MPa, Elongation: 260%, Dry adhesion to glass: 215 g / in.

Example 6 and Comparative Experiment A (which used a similar oligomer backbone) clearly demonstrate that the radiation curable coating compositions according to the present invention, described by dose modulus techniques as well as real-time DMA, cure rapidly.

In addition, Examples 6 to 8, and Comparative Experiment A demonstrate that the adhesion to glass is improved when applying the radiation curable coating composition according to the present invention.

Claims (23)

(A) A compound having a number average molecular weight (Mn) of 500 kg / kmol or more and represented by P- (D- (meth) acrylate) _n [wherein n is 2 to 40 and P is an oligomer or polymer main chain (backbone), and D includes a urethane group and a heterocyclic group, wherein the heterocyclic group has a Boltzmann average dipole moment of 2.5 Debye or more; and (B) A radiation curable coating composition comprising a reactive diluent. The method of claim 1, The heterocyclic group is a radiation curable coating composition, characterized in that the oxazolidone group. (A) a compound containing an oxazolidone group, a urethane group, and a (meth) acrylate group, and having a number average molecular weight (Mn) of 500 kg / kmol or more, and (B) A radiation curable coating composition comprising a reactive diluent. The method according to any one of claims 1 to 3, Compound (A) is a radiation curable coating composition, characterized in that the compound represented by the formula (1) or (2): (Formula 1) (In Formula 1, P is an oligomer or polymer backbone linked with either the 4th or 5th position of oxazolidone, n is 2 to 40, R is H, C ₁ -C ₅ alkyl, R ₁ is C ₁ -C ₃₀ alkyl, cycloalkyl, aryl or alkylaryl, R ₂ is C ₁ -C ₁₂ alkyl, cycloalkyl, aryl, alkylaryl, alkoxy alkyl or alkoxy aryl) (Formula 2) (In Formula 2, P is an oligomer or polymer backbone, n is 2 to 40, R is H, C ₁ -C ₅ alkyl, R ₁ is C ₁ -C ₃₀ alkyl, cycloalkyl, aryl or alkylaryl, R ₂ is C ₁ -C ₁₂ alkyl, cycloalkyl, aryl, alkylaryl, alkoxy alkyl or alkoxy aryl, R ₂ is linked to one of the 4th or 5th positions of oxazolidone) The method according to claim 1, 2 or 4, n is 2 to 10, the radiation curable coating composition. The method of claim 5, wherein n is 2, the radiation curable coating composition. The method according to any one of claims 4 to 6, R is H or CH ₃ radiation curable coating composition. The method according to any one of claims 4 to 7, R ₁ is C ₂ -C ₂₀ alkyl, cycloalkyl, aryl or arylalkyl. The method according to any one of claims 4 to 8, R ₁ is cycloalkyl, radiation curable coating composition. The method of claim 9, R ₁ is cyclohexyl, characterized in that the radiation curable coating composition. The method of claim 9, R ₁ is Radiation curable coating composition, characterized in that. The method according to any one of claims 4 to 11, R ₂ is methyl, ethyl, 1-propyl, 2-propyl, butyl or ethoxyethyl. The method according to any one of claims 4 to 12, R ₁ is And R ₂ is ethyl. As a manufacturing method of the resin composition containing the compound containing an oxazolidone group and a (meth) acrylate group, The method comprises the step of introducing a (meth) acrylate group into a compound, wherein the reaction step is carried out in the presence of an antioxidant. The method of claim 14, The compound is characterized in that it comprises an oxazolidone group, urethane group and (meth) acrylate group. The method according to claim 14 or 15, Antioxidant is a phenolic antioxidant. The method according to any one of claims 14 to 16, During the reaction step of introducing a (meth) acrylate group into the compound, an oxygen or oxygen containing gas mixture is led to the reaction mixture. The method according to any one of claims 14 to 17, And wherein the (meth) acrylate group is introduced to the compound at the end of the reaction step. 20. A resin composition obtainable according to the method of claim 14. Compound represented by the formula (1): (Formula 1) (In Formula 1, P is an oligomer or polymer backbone linked with either the 4th or 5th position of oxazolidone, n is 2 to 40, R is H, C ₁ -C ₅ alkyl, R ₁ is C ₁ -C ₃₀ alkyl, cycloalkyl, aryl or alkylaryl, R ₂ is C ₁ -C ₁₂ alkyl, cycloalkyl, aryl, alkylaryl, alkoxy alkyl or alkoxy aryl) A radiation curable coating composition comprising a radiation curable oligomer, a reactive diluent and a photoinitiator in an amount to exhibit the following properties (i) and (ii) when the composition is cured: (i) the curing time of about 0.11 seconds or less when measured by real-time DMA as the time required for G 'to reach 2 x 10 ⁴ Pa, and (ii) dry adhesion of at least about 250 g / in. Use of the radiation curable coating composition according to any one of claims 1 to 13 and 21 as a composition for a first optical fiber coating material. A coated optical fiber comprising a glass optical fiber, a first coating material and a second coating material when cured, The first coating material comprises the composition according to any one of claims 1 to 13 and 21.